JP2002037770A - Bis(4-mercaptophenyl)sulfide derivative and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin monomer capable of forming a dielectric film suitable for electronic parts and provide a method for producing the resin monomer. SOLUTION: The resin monomer is a bis(4-mercaptophenyl)sulfide derivative expressed by general formula (1) (R is H or methyl; and (n) is an integer of 1-4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bis (4-mercaptophenyl) sulfide derivative and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a resin film has been used as a dielectric film used for a capacitor or the like. Such a dielectric film is disclosed in JP-B-63-32929, JP-A-11-1.
As shown in US Pat. No. 47272 and US Pat. No. 5,125,138, a resin monomer deposited on a substrate is irradiated with an electron beam or ultraviolet rays to cure the resin monomer.

As a resin monomer for forming the dielectric film, for example, a polymerizable vinyl monomer such as dimethylol tricyclodecane diacrylate has been used.

[0004]

However, there has been a problem that electronic components using a dielectric film formed of the above resin monomer have insufficient characteristics. In particular, there has been a problem that electronic components using a dielectric film formed of the above resin monomer have insufficient characteristics at high humidity or high temperature.

[0005] In order to solve the above problems, an object of the present invention is to provide a resin monomer capable of forming a dielectric film suitable for an electronic component and a method for producing the same.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found a new resin monomer. That is, the resin monomer of the present invention,
It is a bis (4-mercaptophenyl) sulfide derivative represented by the following general formula (1).

[0007]

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Wherein R represents hydrogen or a methyl group;
(n represents an integer of 1 or more and 4 or less) The bis (4-mercaptophenyl) sulfide derivative of the present invention is suitable as a resin monomer for forming a dielectric film used for an electronic component.

In the bis (4-mercaptophenyl) sulfide derivative of the present invention, it is preferable that R is hydrogen and n is 2. According to the above configuration, a resin monomer particularly suitable for forming a dielectric film used for an electronic component can be obtained.

Further, the method for producing a bis (4-mercaptophenyl) sulfide derivative of the present invention comprises a bis (4-mercaptophenyl) sulfide represented by the following chemical formula (2) and an ω- having 4 or less carbon atoms. A first step of producing an organic compound represented by the following general formula (3) by reacting with a haloalkyl alcohol; an alkyl acrylate or an alkyl methacrylate; And a second step of producing a bis (4-mercaptophenyl) sulfide derivative represented by the following general formula (1) by reacting the compound with an organic compound.

[0011]

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[0012]

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(Wherein, n represents an integer of 1 or more and 4 or less)

[0014]

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Wherein R represents hydrogen or a methyl group;
According to the method for producing a bis (4-mercaptophenyl) sulfide derivative of the present invention, the resin monomer represented by the general formula (1) can be easily produced.

In the production method of the present invention, the ω-haloalkyl alcohol is 2-haloethanol in the first step, and methyl acrylate is represented by the general formula (3) in the second step. It is preferred to react with the compound. According to the above configuration, a bis (4-mercaptophenyl) sulfide derivative particularly suitable as a resin monomer for forming a dielectric film used for an electronic component can be easily produced.

In the production method of the present invention, the first step is preferably performed in the presence of an alkali metal carbonate as a base catalyst. In addition, the second step is preferably performed in the presence of an alkoxytitanium or organotin compound which is a transesterification catalyst. According to the above configuration, a bis (4-mercaptophenyl) sulfide derivative can be efficiently produced.

[0018]

Embodiments of the present invention will be described below.

Embodiment 1 In Embodiment 1, a bis (4-mercaptophenyl) sulfide derivative of the present invention will be described.

Bis (4-mercaptophenyl) of the present invention
The sulfide derivative is represented by the following general formula (1).

[0021]

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(Wherein R represents hydrogen or a methyl group;
n represents an integer of 1 or more and 4 or less. The bis (4-mercaptophenyl) sulfide derivative of the general formula (1) can be produced by the method described in the second embodiment.

The bis (4-mercaptophenyl) sulfide derivative of the above general formula (1) can be used as a resin monomer for forming a dielectric film used for electronic parts. When a dielectric film is formed using this resin monomer, first, a thin film containing the resin monomer may be formed, and the thin film may be irradiated with an electron beam or ultraviolet light. By using this resin monomer, a dielectric film suitable for an electronic component can be formed. In particular, R in the above general formula (1)
Is hydrogen and the dielectric film of the capacitor is formed using a resin monomer composed of a bis (4-mercaptophenyl) sulfide derivative in which n is 2 so that the characteristics are high even under high humidity and high temperature. A capacitor is obtained.

Embodiment 2 In Embodiment 2, a method for producing the bis (4-mercaptophenyl) sulfide derivative represented by the general formula (1) described in Embodiment 1 will be described.

First, bis (4-mercaptophenyl) sulfide represented by the following chemical formula (2) and an ω-haloalkyl alcohol are reacted with a base as a catalyst at 60 ° C. to 120 ° C.
The reaction is carried out at 4 ° C. for 4 to 8 hours, thereby producing an organic compound represented by the following general formula (3) (first step).

[0026]

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[0027]

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(Wherein, n represents an integer of 1 or more and 4 or less) The bis (4-mercaptophenyl) sulfide represented by the chemical formula (2) is sold by Sumitomo Seika Co., Ltd. under the trade name MPS. ing.

The ω-haloalkyl alcohol used in the first step has a linear carbon chain having 1 to 4 carbon atoms, and has a hydroxyl group at one end of the carbon chain.
This is an alcohol having a halogen at the carbon at the other end of the carbon chain. Specifically, for example, 2-chloroethanol, 3
-Chloro-1-propanol, 4-chloro-1-butanol, 2-bromoethanol, 3-bromo-1-propanol, 2-iodoethanol and the like can be used. In addition, the carbon number of the ω-haloalkyl alcohol is n of the bis (4-mercaptophenyl) sulfide derivative of the general formula (1). For example, when 2-chloroethanol is used, n in the general formula (1) is 2.

The base catalyst used in the first step includes alkali metal carbonates such as Na ₂ CO ₃ and K ₂ CO ₃ , alkaline earth metal carbonates such as CaCO ₃ and MgCO ₃ , and alkali metal carbonates. Are suitable. Of these, alkali metal carbonates are preferred. Suitable solvents for the above base catalyst include ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.

After the first step, the alkyl acrylate or alkyl methacrylate and the organic compound represented by the general formula (3) are refluxed for 6 to 10 hours in the presence of a transesterification catalyst. Bis (4-mercaptophenyl) of the general formula (1)
A sulfide derivative can be produced (second step).

In the second step, the alkyl acrylate (CH ₂ ＣＨCHCOOR ′, and the alkyl group R ′ is, for example, a methyl group, an ethyl group,
A propyl group, a butyl group and the like can be used. ),
Preferably by using methyl acrylate, R
Is hydrogen, a bis (4-mercaptophenyl) sulfide derivative of the general formula (1) is obtained. In addition, methacrylic acid alkyl ester (CH ₂ ＣC (CH ₃ ) COOR ″, and an alkyl group R ″ may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.) By using preferably methyl methacrylate, a bis (4-mercaptophenyl) sulfide derivative of the general formula (1) in which R is a methyl group can be obtained.

As the transesterification catalyst used in the second step, alkoxytitanium such as tetrabutyl titanate and organotin compounds such as dibutyltin oxide, dioctyltin oxide, dibutyltin diacetate and dibutyltin dilaurate are suitable. Among them, tetrabutyl titanate or dibutyl tin oxide is preferable. The amount of the alkyl acrylate (or alkyl methacrylate) to be charged in the second step is preferably 3 to 10 parts by weight based on 1 part by weight of the organic compound of the general formula (3).

In the above production method, the ω-haloalkyl alcohol is 2-haloethanol in the first step, and methyl acrylate is reacted with the compound represented by the general formula (3) in the second step. Is preferred.

According to the production method of the second embodiment, the bis (4-mercaptophenyl) sulfide derivative of the general formula (1) described in the first embodiment can be easily produced.

[0036]

The present invention will be described in more detail with reference to the following examples.

(Example 1) In Example 1, the general formula (1)
An example of preparing a bis (4-acryloyloxyethylenethiophenyl) sulfide in which R is hydrogen and n is 2 among the bis (4-mercaptophenyl) sulfide derivatives represented by In addition, among the bis (4-mercaptophenyl) sulfide derivatives represented by the general formula (1), an example in which bis (4-methacryloyloxybutylenethiophenyl) sulfide in which R is a methyl group and n is 4 is also prepared. explain.

First, 25.0 g of bis (4-mercaptophenyl) sulfide represented by the above chemical formula (2)
(0.10 mol) and 16.1 g of 2-chloroethanol
(0.20 mol) and 27.6 g of potassium carbonate (0.2
0 mol) and 300 ml of methyl isobutyl ketone,
The sample was collected in a flask having a capacity of 1 liter, and reacted by continuing stirring under reflux for 6 hours. After completion of the reaction, 50 ml of 5% hydrochloric acid aqueous solution was gradually added to the obtained solution while stirring, and then 300 ml of toluene was further added. The solution thus obtained was repeatedly washed with distilled water until the pH reached 7. Next, after the solution after washing was dried with anhydrous sodium sulfate, the solvent was distilled off to obtain 32 g of an intermediate product represented by the following chemical formula (4).

[0039]

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Next, 320 g of methyl acrylate and 0.32 g of tetrabutyl titanate (1/100 of the intermediate product) were added to 32 g of the intermediate product represented by the chemical formula (4).
Parts by weight) and 0.16 g (5/1000 parts by weight based on the intermediate product) of p-methoxyphenol as a polymerization inhibitor were added, and the mixture was refluxed for 10 hours, and then methyl acrylate was distilled off. The reaction product thus obtained was dissolved in 300 ml of toluene, and the solution was washed successively with 50 ml of 5% aqueous sodium hydroxide and 50 ml of 5% aqueous hydrochloric acid. Further, the solution was washed with distilled water until the pH reached 7, and then dried using anhydrous sodium sulfate. After 0.16 g of p-methoxyphenol was added to this solution, the solvent was distilled off to obtain a semi-solid having a melting point of 20 ° C. This semi-solid was subjected to infrared spectroscopy (IR) and gel permeation chromatography (GPC) measurements.

FIG. 1 shows the measurement results of IR. As is evident from FIG. 1, 1725c based on acrylate
An absorption peak at m ^-1 is seen. In GPC, no raw materials, intermediate products, and by-products were detected.
From the above, it was found that the finally obtained semi-solid was bis (4-acryloyloxyethylenethiophenyl) sulfide represented by the following chemical formula (5).

[0042]

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Next, among the organic compounds represented by the general formula (1), an example in which bis (4-methacryloyloxybutylenethiophenyl) sulfide in which R is a methyl group and n is 4 will be described.

In this case, the production is carried out in the same manner as in the above production method, except that the raw materials used for the production of bis (4-acryloyloxyethylenethiophenyl) sulfide represented by the chemical formula (5) are changed. it can. Specifically, instead of 2-chloroethanol, 4-chloro-1-
Butanol may be used, and methyl methacrylate may be used instead of methyl acrylate. As a result, bis (4-methacryloyloxybutylenethiophenyl) sulfide represented by the following chemical formula (6) was obtained.

[0045]

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Example 2 In Example 2, an example in which a capacitor was produced using the bis (4-mercaptophenyl) sulfide derivative of the present invention will be described.

FIG. 2 shows a manufacturing process of the capacitor according to the second embodiment. Referring to FIG. 2A, first, the thickness 2
5 μm PET (polyethylene terephthalate) substrate 1
1 was prepared, and a lower electrode film 12 (thickness: 30 nm) made of aluminum was deposited on the PET substrate 11 at a deposition rate of 100 nm / sec.

Thereafter, a thin film 13a (thickness: 200 nm) made of a resin monomer was formed on the lower electrode film 12 by evaporating a resin monomer (see FIG. 2B). Specifically, bis (4-acryloyloxyethylenethiophenyl) sulfide represented by the chemical formula (5) of the present invention is charged into a container 32 as shown in FIG. 3 as the resin monomer 31, and this is charged at 500 nm / sec. Heating was performed at the deposition rate, and a thin film 13a was formed at a position where a part of the lower electrode film 12 was exposed.

Thereafter, the accelerating electrons of -15 kV were applied to 50 μA.
By irradiating the thin film 13a at a density of / cm ² for 2 seconds, the resin monomer in the thin film 13a was polymerized to form the dielectric film 13 (see FIG. 2 (c)).

Thereafter, an upper electrode film 14 made of aluminum was deposited at a deposition rate of 100 nm / sec above the dielectric film 13 and at a position not in contact with the lower electrode film 12 (see FIG. 2D). . The capacitor thus manufactured was referred to as Example Sample 1.

As a comparative example, the following chemical formula (A)
A dimethylol tricyclodecane diacrylate represented by the formula and 1,9-nonanediol diacrylate represented by the chemical formula (B) were used as resin monomers, and a capacitor was produced in the same manner as described above. did.

[0052]

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[0053]

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The characteristics of the above three types of capacitors were evaluated. Specifically, the moisture absorption capacity change rate,
The high-temperature load capacity change rate and the change in the element thickness when the element was immersed in warm water were examined (the details of the measurement method will be described later). Table 1 shows the evaluation results of the capacitors of Working Sample 1, Comparative Sample 1, and Comparative Sample 2.

[0055]

[Table 1]

In Table 1, the rate of change of the high-temperature load capacity
10% or less means that the high-temperature load capacity change rate is negatively larger than -10%.

As is clear from Table 1, the capacitor of the working sample 1 using the resin monomer of the chemical formula (5) of the present invention showed more excellent characteristics than the comparative sample in any of the evaluations. That is, by forming the dielectric film of the capacitor using the resin monomer comprising the bis (4-mercaptophenyl) sulfide derivative of the present invention, a capacitor having excellent characteristics even under high humidity and high temperature can be obtained. . The dielectric loss tangent (ta)
As for nδ), the capacitor of the working sample 1 showed better characteristics than the capacitors of the comparative samples 1 and 2.

Hereinafter, the evaluation methods shown in Table 1 will be described in detail.

The rate of change in moisture absorption capacity was evaluated as follows. First, put the capacitor in a 105 ° C environment.
Dried time was measured initial capacitance C _11. The capacity was measured by applying a sine wave having a frequency of 1 kHz and a voltage of 1 Vrms to a capacitor. Thereafter, the temperature 60 ° C., allowed to stand for 100 hours a capacitor in an environment of humidity 95% Rh, after leaving capacity (capacity at moisture) C _12, was measured under the same conditions as the initial capacity. The rate of change of the moisture absorption capacity is (C ₁₂ −C ₁₁ ) / C ₁₁ × 10
This is a value represented by 0 (%). The smaller the rate of change in the moisture absorption capacity, the higher the capacity stability under a humidity environment, which is preferable as a product. Therefore, it is particularly important that the rate of change in moisture absorption capacity is as small as possible.

The high-temperature load capacity change rate was evaluated as follows. First, the capacitor was dried at 105 ° C. for 10 hours, and the initial capacity C ₃₁ was measured. The capacity was measured by applying a sine wave having a frequency of 1 kHz and a voltage of 1 Vrms to a capacitor. After that, a DC voltage of 16 V was applied to the capacitor in an environment of a temperature of 105 ° C.
And left 000 hours, the capacity C ₃₂ after standing was measured under the same conditions as the initial capacity. High temperature load capacitance change ratio, (C ₃₂ -
C ₃₁ ) / C ₃₁ × 100 (%). The smaller the absolute value of the high-temperature load capacity change rate, the more difficult it is to oxidize at a high temperature, which is preferable as a product. In particular,
In recent years, high-temperature resistance of electronic components has become important as CPU speeds have increased, and the small absolute value of the high-temperature load capacity change rate is an important index for capacitor evaluation.

The change in thickness when immersed in warm water was evaluated as follows. First, the thickness of the capacitor was measured. Next, the capacitor was immersed in hot water of 90 ° C. for 3.5 hours, and then the capacitor was taken out of the hot water and the thickness was measured again. Then, the thickness before immersion in hot water and the thickness after immersion were compared. The greater the change in the thickness, the more the dielectric film absorbs moisture, indicating that the adhesion to the metal electrode film is reduced. Therefore, the smaller the change in thickness, the higher the adhesion between the dielectric film and the electrode film, which is preferable as a product.

The dielectric loss tangent (tan δ) is
A sine wave having a frequency of 1 kHz and a voltage of 1 Vrms was applied to a capacitor and measured. The smaller the dielectric loss tangent, the smaller the power consumed by the capacitor itself, which is preferable as a product.

Although the embodiments of the present invention have been described above by way of examples, the present invention is not limited to the above embodiments, but can be applied to other embodiments based on the technical idea of the present invention. .

[0064]

As described above, the present invention provides a novel bis (4-mercaptophenyl) sulfide derivative represented by the above general formula (1). The bis (4-mercaptophenyl) sulfide derivative of the present invention represented by the general formula (1) can be used for an electronic component, particularly, for example, a capacitor,
It is useful for coils, resistors, capacitive batteries, support members for other electronic components, and the like. By forming a dielectric film using the bis (4-mercaptophenyl) sulfide derivative of the present invention and using it for an electronic component, an electronic component having excellent characteristics even under high humidity and high temperature can be obtained.

According to the method for producing a bis (4-mercaptophenyl) sulfide derivative of the present invention, the bis (4-mercaptophenyl) sulfide derivative represented by the above general formula (1) can be easily produced.

[Brief description of the drawings]

FIG. 1 is a diagram showing an IR spectrum of an example of the bis (4-mercaptophenyl) sulfide derivative of the present invention.

FIG. 2 is a diagram illustrating an example of a manufacturing process in a case where a capacitor is manufactured using the bis (4-mercaptophenyl) sulfide derivative of the present invention.

FIG. 3 is a view showing one step of the manufacturing process shown in FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 Capacitor (electronic component) 11 PET board 12 Lower electrode film 13 Dielectric film 13a Thin film 14 Upper electrode film

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshiaki Kai, 1006 Kadoma Kadoma, Kadoma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (72) Inventor Yu Odori 1006 Kadoma, Kadoma, Kadoma, Osaka Matsushita Electric Industrial Co., Ltd. 72) Inventor Hisaaki Tatehara 1006 Kazuma Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (72) Inventor Hideki Matsuda 1006 Oji Kadoma Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (72) Atsushi Katsune Osaka 1006 Kadoma Kadoma, Matsushita Electric Industrial Co., Ltd. (72) Inventor Kazuo Iwaoka 1006 Kadoma, Kadoma, Osaka Pref. Matsushita Electric Industrial Co., Ltd. (72) Takanori Sugimoto 1006 Kadoma, Kadoma, Osaka Matsushita Matsushita Electric Industrial Co., Ltd. Co., Ltd. in the F-term (reference) 4H006 AA01 AA02 AB78 TA04 TB14 4H039 CA60 CA66 CD10 CD20 CD40

Claims (6)

[Claims] A bis (4) represented by the following general formula (1):
-Mercaptophenyl) sulfide derivatives. Embedded image (Wherein, R represents hydrogen or a methyl group, and n is 1 or more and 4
Indicate the following integer) 2. The bis (4-mercaptophenyl) sulfide derivative according to claim 1, wherein said R is hydrogen and said n is 2. 3. A bis (4) represented by the following chemical formula (2):
(Mercaptophenyl) sulfide and an ω-haloalkyl alcohol having 4 or less carbon atoms to produce an organic compound represented by the following general formula (3): Alternatively, a bis (4-mercaptophenyl) sulfide derivative represented by the following general formula (1) is produced by reacting an alkyl methacrylate with an organic compound represented by the general formula (3). 2. A process for producing a bis (4-mercaptophenyl) sulfide derivative, comprising the steps of: Embedded image Embedded image (Wherein, n represents an integer of 1 or more and 4 or less) (Wherein, R represents hydrogen or a methyl group, and n is 1 or more and 4
Indicate the following integer) 4. In the first step, the ω-haloalkyl alcohol is 2-haloethanol, and in the second step, methyl acrylate is reacted with the organic compound represented by the general formula (3). A method for producing the bis (4-mercaptophenyl) sulfide derivative according to claim 3. 5. The method for producing a bis (4-mercaptophenyl) sulfide derivative according to claim 3, wherein the first step is performed in the presence of an alkali metal carbonate that is a base catalyst. 6. The bis (4- according to claim 3, wherein the second step is performed in the presence of an alkoxytitanium or an organotin compound which is a transesterification catalyst.
A method for producing a (mercaptophenyl) sulfide derivative.